US3754039A - Bicyclic ethers of the cyllododecane series - Google Patents
Bicyclic ethers of the cyllododecane series Download PDFInfo
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- US3754039A US3754039A US00102978A US3754039DA US3754039A US 3754039 A US3754039 A US 3754039A US 00102978 A US00102978 A US 00102978A US 3754039D A US3754039D A US 3754039DA US 3754039 A US3754039 A US 3754039A
- Authority
- US
- United States
- Prior art keywords
- ether
- bicyclo
- solution
- tridec
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- -1 Bicyclic ethers Chemical class 0.000 title abstract description 17
- 239000002304 perfume Substances 0.000 abstract description 4
- 239000000834 fixative Substances 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 41
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 16
- 150000002084 enol ethers Chemical class 0.000 description 14
- 235000019645 odor Nutrition 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 4
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical class C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- HYHDEPUEVHRKEC-UHFFFAOYSA-N 1-methoxybicyclo[10.1.0]tridecane Chemical compound COC12CCCCCCCCCCC2C1 HYHDEPUEVHRKEC-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 3
- 229940052303 ethers for general anesthesia Drugs 0.000 description 3
- 229940035423 ethyl ether Drugs 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JNVXRQOSRUDXDY-UHFFFAOYSA-N 1,1-diiodoethane Chemical compound CC(I)I JNVXRQOSRUDXDY-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 241000218645 Cedrus Species 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229950005228 bromoform Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- WLXALCKAKGDNAT-UHFFFAOYSA-N diazoethane Chemical compound CC=[N+]=[N-] WLXALCKAKGDNAT-UHFFFAOYSA-N 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 230000008570 general process Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BZWJDKJBAVXCMH-UHFFFAOYSA-N 1-diazopropane Chemical compound CCC=[N+]=[N-] BZWJDKJBAVXCMH-UHFFFAOYSA-N 0.000 description 1
- MERVLUJHZNXQQO-UHFFFAOYSA-N 1-ethoxybicyclo[10.1.0]tridecane Chemical compound C(C)OC12CCCCCCCCCCC2C1 MERVLUJHZNXQQO-UHFFFAOYSA-N 0.000 description 1
- QKXCGPJJHMULFJ-UHFFFAOYSA-N 1-methoxycyclododecene Chemical compound COC1=CCCCCCCCCCC1 QKXCGPJJHMULFJ-UHFFFAOYSA-N 0.000 description 1
- UFOUDYPOSJJEDJ-UHFFFAOYSA-N 2-Phenylpropionaldehyde dimethyl acetal Chemical compound COC(OC)C(C)C1=CC=CC=C1 UFOUDYPOSJJEDJ-UHFFFAOYSA-N 0.000 description 1
- NFAVNWJJYQAGNB-UHFFFAOYSA-N 2-methylundecanal Chemical compound CCCCCCCCCC(C)C=O NFAVNWJJYQAGNB-UHFFFAOYSA-N 0.000 description 1
- ZXGMMHMAGOAFGQ-UHFFFAOYSA-N 6-methyl-3-oxa-13-azatetracyclo[7.7.1.02,7.013,17]heptadeca-1(17),2(7),8-trien-4-one Chemical compound C1CCN2CCCC3=C2C1=C1OC(=O)CC(C)C1=C3 ZXGMMHMAGOAFGQ-UHFFFAOYSA-N 0.000 description 1
- 241000717739 Boswellia sacra Species 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- 239000004863 Frankincense Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000000513 Santalum album Species 0.000 description 1
- 235000008632 Santalum album Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 244000284012 Vetiveria zizanioides Species 0.000 description 1
- 235000007769 Vetiveria zizanioides Nutrition 0.000 description 1
- 229910001115 Zinc-copper couple Inorganic materials 0.000 description 1
- JIIYXCYCANOONZ-UHFFFAOYSA-N [Zn]CI Chemical compound [Zn]CI JIIYXCYCANOONZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000002783 ambrette Nutrition 0.000 description 1
- 244000096712 ambrette Species 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- AVLHSKUBJLLTQD-UHFFFAOYSA-N bicyclo[10.1.0]tridecane Chemical class C1CCCCCCCCCC2CC21 AVLHSKUBJLLTQD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229940125890 compound Ia Drugs 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000001299 ferula galbaniflua resinoid Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 235000011929 mousse Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
- C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
- C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms
Definitions
- the present invention is concerned with novel bicyclic ethers of the cyclododecane series of the general formula QCE O 910 wherein R signifies an alkyl group containing 1-4 C-atoms (such as methyl, ethyl, propyl, isopropyl, normal or branched butyl) and R as well as R independently of each other signify hydrogen, methyl or ethyl.
- R signifies an alkyl group containing 1-4 C-atoms (such as methyl, ethyl, propyl, isopropyl, normal or branched butyl) and R as well as R independently of each other signify hydrogen, methyl or ethyl.
- the compounds of General Formula 1 are distinguished by particular odor properties (warm-woody, amberto musk-like notes with good adhesion) on the basis of which they can be used for perfumery purposes such as manufacture of perfumes or for perfuming products of all kinds such as cosmetic articles (soaps, powders, creams, lotions etc.).
- the content of compounds of General Formul I in odorant compostions is governed by the intended use and can vary within wide limits, for example between 0.005-30 wt. percent.
- the compounds of General Formula I can be obtained by (a) Adding to the olefinic double bond of a compound of the general formula wherein -R signifies the same as above, a group of the general formula wherein R and R signfy the same as above, or by (b) Replacing the halogen atoms of a compound of the general formula (III)
- the processes of the present invention may be schematically summarized as follows:
- the enol ether (11) is reacted with a methylidene or ethylidene h'alide such as the iodide in the presence of a zinc/ copper couple by heating under reflux in a solvent. It is preferred to use a slight excess of the halide in the enol ether, an excess of about 10 mole percent is satisfactory, a similar amount and excess of zinc copper couple are also preferably utilized.
- the reaction mixture is taken up in a suitable solvent, preferably a slightly polar non-hydroxylic solventsuch as diethylether and heated under reflux until an exothermic reaction is noted (ca. 3060 minutes).
- the enol ether (II) is. reacted with a his haloalkyl zinc preferably in the concentrated solution in a solvent, preferably in the presence of a Zll'lC halide catalyst.
- a his haloalkyl zinc preferably in the concentrated solution in a solvent, preferably in the presence of a Zll'lC halide catalyst.
- bis halomethyl-, bis haloethylor bishalopropylzinc Among the aforementioned groups, bisiodomethyl zinc gives the most satisfactory results (Ib)
- an excess of olefin (the unreacted portion being recovered) a ratio of between 1 and 4 moles of olefin per mole of bis iodomethyl zinc being preferred. While the reaction will take place at ambient temperature it is preferred to warm the reaction mixture for from 2-5 hours at between 30-40 C. in a small amount of a solvent such as ether.
- the yield of product is substantially enhanced by the addition of the corresponding Zinc halide, from about 3 to about 6 moles of zinc halide per mole of bis haloalkyl zinc may be usefully employed.
- the desired product is isolated by fractional distillation of the reaction product (see Wittig et al. Ber. 97, 2146, (1964)).
- compound (II) and a moderate excess such as to 30 suitably a 25% molar excess of diethyl zinc in a reaction inert solvent, suitably a hydrocarbon solvent such as petroleum ether is agitated in an inert atmosphere at ambient temperature a substantial excess, say a l to 1.5 molar excess of ethylidene iodide, is slowly added, the mixture allowed to stand for from about 5 to about 12 hours at ambient temperature, the mixture is then quenched with dilute aqueous acid and the product extracted in the usual manner (Nishimura et al., Tetrahedron 25, 2647 (1969)).
- the enol ether (II) is treated with an ethereal solution of an appropriate diazoalkane in the presence of cupric ion.
- the enol ether (II) is mixed with a catalytic amount, suitably between about 5 and about weight percent of anhydrous cupric salt suitably anhydrous cupric sulfate and cooled, suitably to ice-bath temperatures.
- a catalytic amount suitably between about 5 and about weight percent of anhydrous cupric salt suitably anhydrous cupric sulfate
- anhydrous cupric salt suitably anhydrous cupric sulfate
- the rate of addition is controlled to maintain the reaction mixture at ice-bath temperatures, but after addition is complete the mixture is allowed to stand, with agitation, at ambient temperatures.
- the reaction mixture is then worked up in the usual manner.
- the diazoalkanes are prepared in accordance with the method of Wilds et al. J. Org. Chem. 13,, 770 (1948)).
- the general process modification (b) may be carried out by replacement of the gem-dihalo starting material halogens with hydrogen, methyl or ethyl.
- the appropriate enol-ether (II) is converted into the corresponding 13,13- dihalo-bicyclo[10.1.01tridec-l-yl ether by reaction with either chloroform or bromoform in accordance with the method set forth in Parham and Sperley (J. Org. Chem. 32, 924 (1967)).
- the reduction of the gemhalogen atoms to yield the corresponding bicyclo[10.l.0]tridec-1-yl ether (I) may be achieved either by reduction with nascent hydrogen or by a chemical reduction.
- the source of nascent hydrogen should be generated in a basic medium.
- an alkali metal such as sodium, potassium, or lithium in liquid ammonia may be employed, or one of these metals in an alkanol suitably a lower alkanol, preferably sodium or potassium in ethanol may be used.
- other reduction may be achieved with trialkyltinhydride or electrolytic reduction in a basic medium. Especially preferred is the reduction employing sodium in liquid ammonia.
- the sodium and liquid ammonia reduction is carried out by preparing a solution of sodium in dry liquid ammonia. It is desirable to use a substantial excess of sodium suitably an excess of the order of from about 5 to about 4 7 moles of sodium per mole of dihalo ether (IV). Th liquid ammonia solution is held to a temperature of from about 40 to about 50 C. and the dihalo ether (1V) is added slowly thereto. After addition is complete, the mixture is agitated for about 1 hour, and the excess alkali metal neutralized by careful addition of pulverized ammonium chloride. The quenched reaction mixture is stirred for a further hour, the ammonia permitted to evaporate, and the desired product isolated by Work-up in the usual manner.
- a substantial excess of sodium suitably an excess of the order of from about 5 to about 4 7 moles of sodium per mole of dihalo ether (IV).
- Th liquid ammonia solution is held to a temperature of from about 40 to about 50 C. and the dihalo ether (1V) is
- the dihalo compound (IV) may be reacted in such a manner as to substitute the halo atoms by an alkyl group to give a compound of General Formula Ic.
- the reagent utilized is a lithium dialkyl copper which is obtained by reacting the appropriate alkyl lithium with cuprous iodide in a molar ratio of 2:1.
- an ethereal solution of the appropriate alkyl lithium suitably methyl lithium or ethyl lithium is added under an inert atmosphere to a suspension of cuprous iodide in dry ethyl ether.
- the solution is cooled to from about l0 to about +5 C. suitably to about 5 to 0 C. and an ethereal solution of the dihalo-preferably the dibromo-bicyclo[10.1.01tridec 1 yl ether in ethyl ether added slowly thereto.
- reaction mixture is stirred for from about 8 to about 12 hours at ambient temperature, and quenched by pouring into a cold, aqueous solution of ammonium chloride.
- the resultant mixture is exhaustively extracted with ether, and the desired product isolated therefrom by fractional distillation in the usual manner.
- the novel odorant compositions produced in accordance with the present invention which have excellent fixative properties, may be utilized in a wide range of proportions in compositions containing them. Preferably, however, they are utilized in amounts ranging from about 0.5 to about 20% by weight in the compositions comprising them. And, for example, when utilized for the perfuming of soaps, between 1 and 2% by weight of such perfume compositions will sufiice. In compositions such as lotions, suitably hand lotions and the like, from between 2 to about 3% by weight of such compositions are utilized and in bath salts and essences, depending on the type of composition, between 0.3 and 5% by weight of the composition are utilized. It should be noted that a rather special interest among the novel odorant compounds of the present invention is bicyclo[10.l.0]tridec1-yl-methyl ether having a woody-warm amber-like odor.
- Example I (a) 9.8 g. of zinc-copper alloy (see Organic Syntheses, vol. 41 (1961), 72) are stirred with a few crystals of iodine for ca. 15 minutes in 100 ml. of absolute ether until the iodine color disappears. 9.86 g. of l-methoxy-lcyclododecene and 40.2 g. of freshly distilled methylene iodide are thereupon rapidly added. The mixture is heated under reflux in nitrogen atmosphere with good stirring for 48 hours.
- Example II According to the process described in Example I or in the following Example III, but using l-ethoxy-l-cyclododecene as the starting material, there is obtained bicyclo [10.1.0]tridec-1-yl ethylether.
- Example III 400 ml. of an ethereal diazoethane solution (manufactured according to A. L. Wilds et al., J. Org. Chem. 13 (1948) 770) are added dropwise within 30 minutes with ice-cooling and stirring to 16.6 g. of l-methoxy-l-cyclododecene and 1 g. of anhydrous copper (H) sulphate. Overnight, the mixture is further stirred at room temperature. The ethereal solution is then dried with a little anhydrous magnesium sulphate, filtered and evaporated. The resulting oily crude product (17.9 g.) is chromatographed on the 50-fold amount by Weight of silica gel.
- H copper
- Example IV (a) A solution of 94 g. of 13,13-dichloro-bicyclo- [10.1.0]tridec-1-yl methyl ether in 500 ml. of abs. ether is slowly added dropwise at 40 to --50 to 47 g. of sodium dissolved in 1 litre of liquid dry ammonia. After completed addition, the mixture is further stirred for an hour at this temperature, then 168 g. of ammonium chloride (pulverized) are introduced portionwise. After stirring for ca. 1 hour, the ammonia is evaporated off and ca. 1 litre of water is added to the residue. This is sub sequently exhaustively extracted with hexane, the hexane phases are washed neutral and dried in conventional manner.
- Example V (a) 50 ml. of a 1.47 molar ethereal solution of methyl lithium is added under a nitrogen atmosphere to 5.7 g. of copper [I] iodide in 50 ml. of abs. ether. After the sediment has gone into solution, a solution of 13,13- dibromo bicyclo[10.1.0]tridec-1-yl methyl ether in ml. of abs. ether is added dropwise at 5 to 0. The formation of a yellow precipitate is observed. After completion of the addition, the reaction mixture is stirred overnight at room temperature, thereupon poured into ice cold 20% ammonium chloride solution and exhaustively extracted with ether.
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Abstract
THERE ARE PRROVIDED NOVEL BICYCLO (10.1.0) TRIDEC-1-YL ALKYL ETHERS WHICH POSSESS WOODY AMBER LIKE ODORRS AND ARE USEFUL IN THE PERFUME ARTS ON THE VBASIS OF THEIR ODORS AND FIXATIVE PROPERTIES.
Description
States-'PatentOflk 3,754,039 Patented Aug. 21, 1973 US. Cl. 260-611 F 5 Claims ABSTRACT OF THE DISCLOSURE There are provided novel bicyclo [10.1.0] tridec-l-yl alkyl ethers which possess woody amber like odors and are useful in the perfume arts on the basis of their odors and fixative properties.
FIELD OF THE INVENTION Novel odoriferous bicyclic ethers.
RELATED APPLICATIONS This application claims priority from applicants Swiss application 515/70, filed Jan. 15, 1970.
DESCRIPTION OF THE PRIOR ART Certain derivatives of cyclo dodecane are known to have odorant properties. Ethyl 4,8-cyclo dodecadiene-lcarboxylate has a woody, vetiver oil-like odor (DAS 1,223,974 to Procter and Gamble). Ketals of cyclododecanone possess odors reminiscent of cedar and sandalwood with musk and ambrette notes (Swiss Pat. 435,521 to Haarrnann and Reimer) and certain ethers of cyclododecanol possess cedar and mus-k odors. (Swiss Pat. 443,536 to Haarmann and Reimer.)
While bicyclo [10.1.0] tridecane derivatives have been prepared (see Pharham and Sperley, J. Org. Chem. 32 924 (1967)) the l3-alkyl-l-ether derivatives have not been prepared heretofore and nothing was heretofore known about the odor properties of this class of compounds.
The present invention is concerned with novel bicyclic ethers of the cyclododecane series of the general formula QCE O 910 wherein R signifies an alkyl group containing 1-4 C-atoms (such as methyl, ethyl, propyl, isopropyl, normal or branched butyl) and R as well as R independently of each other signify hydrogen, methyl or ethyl.
The compounds of General Formula 1 are distinguished by particular odor properties (warm-woody, amberto musk-like notes with good adhesion) on the basis of which they can be used for perfumery purposes such as manufacture of perfumes or for perfuming products of all kinds such as cosmetic articles (soaps, powders, creams, lotions etc.). The content of compounds of General Formul I in odorant compostions is governed by the intended use and can vary within wide limits, for example between 0.005-30 wt. percent.
The compounds of General Formula I can be obtained by (a) Adding to the olefinic double bond of a compound of the general formula wherein -R signifies the same as above, a group of the general formula wherein R and R signfy the same as above, or by (b) Replacing the halogen atoms of a compound of the general formula (III) The processes of the present invention may be schematically summarized as follows:
i? CH2C 910 (a) where R =R (b) where R and R =H DESCRIPTION OF THE PREFERRED EMBODIMENTS Several modifications of general process (a) involving addition across the double bond of an enol ether are available.
In one mode of the enol ether (11) is reacted with a methylidene or ethylidene h'alide such as the iodide in the presence of a zinc/ copper couple by heating under reflux in a solvent. It is preferred to use a slight excess of the halide in the enol ether, an excess of about 10 mole percent is satisfactory, a similar amount and excess of zinc copper couple are also preferably utilized. The reaction mixture is taken up in a suitable solvent, preferably a slightly polar non-hydroxylic solventsuch as diethylether and heated under reflux until an exothermic reaction is noted (ca. 3060 minutes). The heat source is removed and the mixture stirred at ambient temperature for from about 10 to about 20, suitably fo about 15 hours and the metallic residue removed, suitably by filtration. The solution is worked up in the usual manner to yield the desired compound (Ia) where R is hydrogen or methyl (see R. D. Smith and H. E. Simmons Org. Synth. 41 72 (1961)).
In another modification the enol ether (II) is. reacted with a his haloalkyl zinc preferably in the concentrated solution in a solvent, preferably in the presence of a Zll'lC halide catalyst. Depending on the product desired there may be utilized bis halomethyl-, bis haloethylor bishalopropylzinc. Among the aforementioned groups, bisiodomethyl zinc gives the most satisfactory results (Ib) There is utilized an excess of olefin (the unreacted portion being recovered) a ratio of between 1 and 4 moles of olefin per mole of bis iodomethyl zinc being preferred. While the reaction will take place at ambient temperature it is preferred to warm the reaction mixture for from 2-5 hours at between 30-40 C. in a small amount of a solvent such as ether.
The yield of product is substantially enhanced by the addition of the corresponding Zinc halide, from about 3 to about 6 moles of zinc halide per mole of bis haloalkyl zinc may be usefully employed. The desired product is isolated by fractional distillation of the reaction product (see Wittig et al. Ber. 97, 2146, (1964)).
In another modification compound Ia (R =H, R =CH may be prepared by reacting compound (II) with ethylidene iodide in the presence of diethyl zinc. In the process compound (II) and a moderate excess such as to 30 suitably a 25% molar excess of diethyl zinc in a reaction inert solvent, suitably a hydrocarbon solvent such as petroleum ether is agitated in an inert atmosphere at ambient temperature a substantial excess, say a l to 1.5 molar excess of ethylidene iodide, is slowly added, the mixture allowed to stand for from about 5 to about 12 hours at ambient temperature, the mixture is then quenched with dilute aqueous acid and the product extracted in the usual manner (Nishimura et al., Tetrahedron 25, 2647 (1969)).
In yet a further embodiment of this modification of the process, the enol ether (II) is treated with an ethereal solution of an appropriate diazoalkane in the presence of cupric ion. In this process, the enol ether (II), is mixed with a catalytic amount, suitably between about 5 and about weight percent of anhydrous cupric salt suitably anhydrous cupric sulfate and cooled, suitably to ice-bath temperatures. There is then slowly added thereto, a substantial excess of the appropriate diazoalkane for example diazomethane, diazoethane or diazopropane, in ethereal solution. The rate of addition is controlled to maintain the reaction mixture at ice-bath temperatures, but after addition is complete the mixture is allowed to stand, with agitation, at ambient temperatures. The reaction mixture is then worked up in the usual manner. (The diazoalkanes are prepared in accordance with the method of Wilds et al. J. Org. Chem. 13,, 770 (1948)).
The general process modification (b) may be carried out by replacement of the gem-dihalo starting material halogens with hydrogen, methyl or ethyl. The appropriate enol-ether (II) is converted into the corresponding 13,13- dihalo-bicyclo[10.1.01tridec-l-yl ether by reaction with either chloroform or bromoform in accordance with the method set forth in Parham and Sperley (J. Org. Chem. 32, 924 (1967)).
The reduction of the gemhalogen atoms to yield the corresponding bicyclo[10.l.0]tridec-1-yl ether (I) may be achieved either by reduction with nascent hydrogen or by a chemical reduction.
In the first mode the source of nascent hydrogen should be generated in a basic medium. Thus, an alkali metal such as sodium, potassium, or lithium in liquid ammonia may be employed, or one of these metals in an alkanol suitably a lower alkanol, preferably sodium or potassium in ethanol may be used. Alternatively, other reduction may be achieved with trialkyltinhydride or electrolytic reduction in a basic medium. Especially preferred is the reduction employing sodium in liquid ammonia.
The sodium and liquid ammonia reduction is carried out by preparing a solution of sodium in dry liquid ammonia. It is desirable to use a substantial excess of sodium suitably an excess of the order of from about 5 to about 4 7 moles of sodium per mole of dihalo ether (IV). Th liquid ammonia solution is held to a temperature of from about 40 to about 50 C. and the dihalo ether (1V) is added slowly thereto. After addition is complete, the mixture is agitated for about 1 hour, and the excess alkali metal neutralized by careful addition of pulverized ammonium chloride. The quenched reaction mixture is stirred for a further hour, the ammonia permitted to evaporate, and the desired product isolated by Work-up in the usual manner.
Alternatively, the dihalo compound (IV) may be reacted in such a manner as to substitute the halo atoms by an alkyl group to give a compound of General Formula Ic. In this mode the reagent utilized is a lithium dialkyl copper which is obtained by reacting the appropriate alkyl lithium with cuprous iodide in a molar ratio of 2:1.
In this modification of the process an ethereal solution of the appropriate alkyl lithium suitably methyl lithium or ethyl lithium is added under an inert atmosphere to a suspension of cuprous iodide in dry ethyl ether. Upon conversion of the suspension to a solution, the solution is cooled to from about l0 to about +5 C. suitably to about 5 to 0 C. and an ethereal solution of the dihalo-preferably the dibromo-bicyclo[10.1.01tridec 1 yl ether in ethyl ether added slowly thereto. After completion of the addition, the reaction mixture is stirred for from about 8 to about 12 hours at ambient temperature, and quenched by pouring into a cold, aqueous solution of ammonium chloride. The resultant mixture is exhaustively extracted with ether, and the desired product isolated therefrom by fractional distillation in the usual manner.
As stated hereinabove, the novel odorant compositions produced in accordance with the present invention which have excellent fixative properties, may be utilized in a wide range of proportions in compositions containing them. Preferably, however, they are utilized in amounts ranging from about 0.5 to about 20% by weight in the compositions comprising them. And, for example, when utilized for the perfuming of soaps, between 1 and 2% by weight of such perfume compositions will sufiice. In compositions such as lotions, suitably hand lotions and the like, from between 2 to about 3% by weight of such compositions are utilized and in bath salts and essences, depending on the type of composition, between 0.3 and 5% by weight of the composition are utilized. It should be noted that a rather special interest among the novel odorant compounds of the present invention is bicyclo[10.l.0]tridec1-yl-methyl ether having a woody-warm amber-like odor.
In the following examples all temperatures are in degrees centigrade C.).
Example I (a) 9.8 g. of zinc-copper alloy (see Organic Syntheses, vol. 41 (1961), 72) are stirred with a few crystals of iodine for ca. 15 minutes in 100 ml. of absolute ether until the iodine color disappears. 9.86 g. of l-methoxy-lcyclododecene and 40.2 g. of freshly distilled methylene iodide are thereupon rapidly added. The mixture is heated under reflux in nitrogen atmosphere with good stirring for 48 hours. Filtration from the residue, rinsing thereof With a large amount of ether, thereupon washing of the combined ether phases three times with saturated ammonium chloride solution and subsequently with saturated bicarbonate solution give, after drying and concentration, 11 g. of a product which is distilled at /0.00l mm. Hg, 11 1.48251.4830.
Analysis.-Calcd. (percent): C, 79.33; H, 12.46. Found (percent): C, 80.09; H, 12.52.
The bicyclo [10.1.0]tridec-1-yl methylether thus obtained (Formula I: R=CH R =H, R =I-I) is disdistinguished by a woody, warm, amber-like odor note.
1070, 995 cmr NMR s[3I-I] at :3.22 p.p.m. cyclopropyl hydrogen between 6:02 p.p.m. and 1.1 p.p.m.
(b) The l-methoxy-l-cyclododecene used as the starting material can be manufactured as follows:
182 g. of cyclododecanone and 117 g. of orthoformic acid trimethyl ester are heated with stirring to 40 until a clear yellowish solution exists. 1 ml. of cone. sulphuric acid is thereupon added dropwise and the mixture is immediately cooled to 20. The solution is subsequently stirred at room temperature for a further 15-20 hours. After the addition of 3 ml. of triethylamine, the product is fractionated in vacuum. Yield of l-methoxy-l-cyclododecene: over 90%.
Example II According to the process described in Example I or in the following Example III, but using l-ethoxy-l-cyclododecene as the starting material, there is obtained bicyclo [10.1.0]tridec-1-yl ethylether.
AnaIysis.Calcd. (percent): C, 80.29; H, 12.80. Found (percent): C, 80.22; H, 12.70. B.p. 90/0.01 mm. Hg.
cmr
NMR m(2H) at 5=3.03.99 p.p.m.; t(3H, J=7
c.p.s.) at 6:1.07 p.p.m.; cyclopropane hydrogen between 6=0.20.4 p.p.m.
The odor of this product displays the woody/amber-like note of the methyl ether described in Example I, but is somewhat weaker.
Example III 400 ml. of an ethereal diazoethane solution (manufactured according to A. L. Wilds et al., J. Org. Chem. 13 (1948) 770) are added dropwise within 30 minutes with ice-cooling and stirring to 16.6 g. of l-methoxy-l-cyclododecene and 1 g. of anhydrous copper (H) sulphate. Overnight, the mixture is further stirred at room temperature. The ethereal solution is then dried with a little anhydrous magnesium sulphate, filtered and evaporated. The resulting oily crude product (17.9 g.) is chromatographed on the 50-fold amount by Weight of silica gel. The desired product is eluted with benzene and further purified by preparative gas chromatography. The odor of the 13-methyl-bicyclo [10.1.0]tridec-1-yl methyl ether (Formula I: R=CH R =H, R =CH thus obtained is weakly woody, musk-like.
NMR s[3H] at 6:32 p.p.m. d[3H] at 6:1.20
p.p.m. cyclopropyl H at 6:005 to 1.0 p.p.m.
Example IV (a) A solution of 94 g. of 13,13-dichloro-bicyclo- [10.1.0]tridec-1-yl methyl ether in 500 ml. of abs. ether is slowly added dropwise at 40 to --50 to 47 g. of sodium dissolved in 1 litre of liquid dry ammonia. After completed addition, the mixture is further stirred for an hour at this temperature, then 168 g. of ammonium chloride (pulverized) are introduced portionwise. After stirring for ca. 1 hour, the ammonia is evaporated off and ca. 1 litre of water is added to the residue. This is sub sequently exhaustively extracted with hexane, the hexane phases are washed neutral and dried in conventional manner. After evaporation of the hexane solution, the bicyclo [10.1.0]tridec-1-yl methyl ether obtained is fractionated in vacuum. B.P.: 85/0.2 mm. Hg. Yield: 36 g. n =1.48251.4830.
(b) The 13,13 dichloro-bicyclo[10.1.0]tridec 1 yl methyl ether used as the starting material can be ob tained as follows:
448 g. of ground potassium hydroxide are mixed with 1.2 litres of absolute 1,2-dimethoxyethane. 80 g. of 1- methoxy-l-cyclododecene are added to the mixture and then 480 g. of chloroform are added dropwise in the course of 8 or more hours with good stirring and with cooling to -15 to 5. After the reaction has subsided, the crude mixture is poured onto ca. 1 kg. of ice and treated with 20% hydrochloric acid up to the neutral point. The product is thereupon filtered off through a filter aid, the filter cake rinsed with 500 ml. of hexane and the filtrate extracted twice with 500 ml. of hexane. The hexane phases are washed with water, dried with sodium sulphate and, after filtration, allowed to run through 230 g. of silica gel (0.3 mm.). After evaporation of the hexane eluates, there are obtained g. of 13,13-dichloro-bicyclo- [10.1.0]tridec-1-yl methyl ether (Formula IV: R=CH X=Cl) in a yield of ca. 83%.
Example V (a) 50 ml. of a 1.47 molar ethereal solution of methyl lithium is added under a nitrogen atmosphere to 5.7 g. of copper [I] iodide in 50 ml. of abs. ether. After the sediment has gone into solution, a solution of 13,13- dibromo bicyclo[10.1.0]tridec-1-yl methyl ether in ml. of abs. ether is added dropwise at 5 to 0. The formation of a yellow precipitate is observed. After completion of the addition, the reaction mixture is stirred overnight at room temperature, thereupon poured into ice cold 20% ammonium chloride solution and exhaustively extracted with ether. After the usual washing neutral with water and drying with magnesium sulphate, after evaporating off the solvent there remain 6 g. of a brown oil which is chromatographed on the 80-fold amount by weight of Florisil. By elution with hexane/ benzene mixtures there is obtained the desired 13,13-dimethyl-bicyclo- [10.1.0]tridec-1-yl methyl ether which is distilled at 80/ 0.001 mm. Hg. The odor is weakly woody.
IR 1475, 1450, 1375, 1086 cm.- NMR s[3H] at 6:325 p.p.m. 2 s [each 3H] at 1.18 p.p.m. and 0.92 p.p.m., m [1H] at 6:0.3 to 0.7 p.p.m.
(b) The 13,13 dibromo-bicyclo[10.1.0]tridec 1 yl methyl ether used as the starting material can be obtained in ca. 70% yield in the manner described in Example HI(b), with the substitution of the chloroform by bromoform.
Example VI Composition (woody-earthy base) with a content of bicyclo[10.1.0]tridec-l-yl methyl ether (Formula I: R=CH3, R1=H, R2==H).
Parts by weight Hydratropaldehyde dimethyl acetal 5 Patachouli oil 25 Galbanum resinoid 20 Olibanum resinoid 15 Mousse de Cherie sol 10 Coumarin 10 Vetiver oil bourbon 20 Methylnonylacetaldehyde (10% in phthalic acid di I claim: 1. A compound of the general formula wherein R signifies an alkyl group containing 1-4 C- References Cited atoms and R as well as R independently of each other signify hydrogen, methyl or ethyl.
2. Bicyclo[10.1.01tridec-l-yl methyl ether, being a compound according to claim 1. 5
3. Bicyclo[10.1.01tridec-1-yl ethyl ether, being a com- BERNARD HELFIN, Primary Examiner pound according to claim 1.
4. l3-methyl-bicyclo[10.1.0]tridec 1 yl methyl ether, U 5 CI X R being a compound according to claim 1.
5. 13,13-dimethyl-bicyclo[10.1.0]tridec 1 yl methyl 10 252-522; 260-611 R ether, being a compound according to claim 1.
Parham et al.: Jour. Org. Chem, vol. 32 (1967), pp.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION A 1 o Patent NO. Dated r 1 7-4 eter I p Inventor(s) I 3 91s.
It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 1, line 4: Inventor's name is Naegeli (not Nageli) Column 1, line 26: "cyclo dodecane" should be "cyclododecane".
Column 1, line 27:. "4, 8-'-cyclo dodecadiene-lear'boxylate", should be "4, 8-cyclododecadiene-l-carboxylate" Column 1, line 36: name is "Parham" not "Pharham".
Column 1, line 61: "Formula" not "Formul".
Column 2, line 23: (b)R CHX /(R CH Zn" not (b) R1CHX2/ (R CH Zn 2 Column 2, line 48: "R =H" not "R =R".
Column 5, line 2: "d" O.2 p.p.m." not "6 0.2 p.p.m.
' Column 5, line 20= 12.58" not "H, 12.80".
Column 5, line 23: cm. not "cm.
Signed and. sealed this 1st 6217- of .pr. 1.975.
n ARsEAL-L m mu o MASON Commissioner o Pa MWLMHPQ Off-Piggy Trademarks F ORM PO-IOSO (IO-e9) USCOMM DC 603760 69 UIS GOVERNMENT PRINTING OFFICE: e 9. 9 o
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US00102978A Expired - Lifetime US3754039A (en) | 1970-12-30 | 1970-12-30 | Bicyclic ethers of the cyllododecane series |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3876561A (en) * | 1970-11-03 | 1975-04-08 | Givauden Corp | Novel odorant cyclododecyl ethers |
US4601851A (en) * | 1983-01-07 | 1986-07-22 | Huels Aktiengesellschaft | Cyclododec-2-enyl ethers in fragrance compositions |
WO2006005874A1 (en) * | 2004-06-21 | 2006-01-19 | Essilor International (Compagnie Generale D'optique) | Polymerisable composition containing an odour masking agent and a perfume, an optical lens and a production method |
EP1790629A1 (en) * | 2005-11-23 | 2007-05-30 | INTERNATIONAL FLAVORS & FRAGRANCES, INC. | Derivatives of octahydro-cycloprop-indene and their use in perfume compositions |
-
1970
- 1970-12-30 US US00102978A patent/US3754039A/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3876561A (en) * | 1970-11-03 | 1975-04-08 | Givauden Corp | Novel odorant cyclododecyl ethers |
US4601851A (en) * | 1983-01-07 | 1986-07-22 | Huels Aktiengesellschaft | Cyclododec-2-enyl ethers in fragrance compositions |
WO2006005874A1 (en) * | 2004-06-21 | 2006-01-19 | Essilor International (Compagnie Generale D'optique) | Polymerisable composition containing an odour masking agent and a perfume, an optical lens and a production method |
US20080013042A1 (en) * | 2004-06-21 | 2008-01-17 | Chefik Habassi | Polymerizable Composition Containing An Odor Masking Agent And A Perfume, An Optical Lens And A Production Method |
US7618141B2 (en) | 2004-06-21 | 2009-11-17 | Essilor International (Compagnie Generale D'optique) | Polymerizable composition containing an odor masking agent and a perfume, an optical lens and a production method |
EP1790629A1 (en) * | 2005-11-23 | 2007-05-30 | INTERNATIONAL FLAVORS & FRAGRANCES, INC. | Derivatives of octahydro-cycloprop-indene and their use in perfume compositions |
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